Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
The Chemical Society of Japan Award for Young Chemists for 2010
Exploration of Boundary between Charge-Density-Wave and Mott–Hubbard States in Quasi-One-Dimensional Halogen-Bridged Metal Complexes
Shinya Takaishi
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2012 Volume 85 Issue 2 Pages 169-180

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Abstract

In spite of a long history of quasi-one-dimensional halogen-bridged complexes (MX-chains), all Pt and Pd complexes form charge-density-wave (CDW) state (–X···M2+···X–M4+–X···), while all Ni complexes form Mott–Hubbard (MH) state (–X–Ni3+–X–Ni3+–X–), without exception. Although an interesting charge dynamics are expected at the boundary between the two states, no compound thus far reported forms both states. Thus, we have sought a phase boundary in bromo-bridged Pd compounds by decreasing Pd···Pd distance. In this article, we introduce the following two methods to decrease Pd···Pd distances: introduction of long alkyl chains which can afford attractive force between them, and partial substitution with smaller Ni ions, [Ni1−xPdx(chxn)2Br]Br2. In both systems, we have succeeded in realizing Pd3+ MH state. It has been revealed that the electronic state of bromo-bridged Pd compounds is determined by the Pd···Pd distances, in other words, CDW and MH states are stabilized when Pd···Pd distances are longer and shorter than 5.26 Å, respectively.

We have quested for phase boundary in bromo-bridged Pd compounds by decreasing Pd···Pd distance by using chemical pressure. It has been revealed that CDW and MH states are stabilized when Pd···Pd distances is longer and shorter than 5.26 Å. Fullsize Image
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© 2012 The Chemical Society of Japan
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